Barbiturate 3-n-methylchorides

ABSTRACT

Barbiturate phosphates characterized by the following structural formula:   WHEREIN R1 and R2 are each selected from the group consisting of C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 alkyl, C3-C6 alkoxyalkyl, phenyl, phenoxy, thiophenyl, wherein said groups can be optionally substituted with chlorine, bromine, nitrile or nitro; R1 and R2 may or may not be the same; R3 is one selected from the group consisting of hydrogen, C1-C6 alkyl, optionally substituted with chlorine or bromine; R4 is one selected from the group consisting of hydrogen, C1-C6 alkyl, optionally substituted with chlorine or bromine, phenyl, bromo or chloro-substituted phenyl, C1-C4 alkylamino, C2-C4 dialkylamino, C2-C4 acyl, C1-C4 thioalkyl, C1-C4 alkylsulfoxide, C1-C4 alkylsulfone, C2-C4 alkoxyalkyl, C2-C6 alkenyl, C3-C6 alkynyl; R5 and R6 are each selected from the group consisting of C1-C6 alkyl, phenyl, C1-C6 chloro or bromo-substituted alkyl, C1-C4 alkylthio, thiophenyl optionally substituted by chlorine, bromine, C1-C4 alkyl or nitro, C1-C4alkylsulfoxide, C1-C4 alkylsulfonyl, C1-C4 alkoxy, C2-C5 alkoxyalkyl, C1-C6 monoalkylamino and C2-C6 dialkyl amino, cyano, thiocyano, C2-C6 alkenyl, C3-C6 alkynyl, nitro, C3-C6 cycloalkyl and C5-C6 cycloalkenyl wherein R5 and R6 may or may not be the same; X and Y can be O or S; and n is an integer ranging from 1 to 3. Such compounds have been found to possess highly active contact and systemic insecticidal and miticidal activity.

United States Patent 1191 Gorbaty I 1111 3,839,335 1451 Oct. 1, 1974 BARBITURATE B-N-METHYLCHORIDES Martin L. Gorbaty, Elizabeth, NJ,

[73] Assignee: Esso Research and Engineering Company 22 Filed: May 19, 1972 21 Appl. N01: 255,126

Related US. Application Data [75] Inventor:

[62] Division of Ser. No. 36,430, May 11, 1970, Pat. No.

52 u.s.c1. "260/257 1511 1111,01 ..C07d 51/20 158 Field ofSearch 260/257, 260, 256.4

[56] References Cited I UNITED STATES PATENTS 2,344,459 3/1944 Henze 260/257- Primary Examiner-Donald G. Daus Assistant Examiner-Anne Marie T. Tighe [5 7']' ABSTRACT Barbiturate phosphates characterized by the following structural formula:

R; ii R2 wherein R and R are each selected from the group consisting of C,C. alkoxy, C,C thioalkyl, C C alkyl, C C,, alkoxyalkyl, phenyl, phenoxy, thiophenyl, wherein said groups can be optionally substituted with chlorine, bromine, nitrile or nitro; R and R mayor may not be the same; R is one selected from the group consisting of hydrogen, C -C alkyl, optionally substituted with chlorine or bromine; R is one selected from the group consisting of hydrogen, C C I nitro, C,-C alkylsulfoxide, C -C alkylsulfonyl, C -C alkoxy, C C alkoxyalkyl, C -C monoalkylamino and C -C5 dialkyl amino, cyano, thiocyano, C -C alkenyl, C -,C alkynyl, nitro, C C cycloalkyl and C C cycloalkenyl wherein R and R may or may not be the same; X and Y can be 0 or S; and n is an integer ranging from 1 to 3. Such compounds have been found to possess highly active contact and systemic insecticidal and miticidal activity.

3 Claims, No Drawings 1 BABEI AIE -rMWET Y This ia a division of application Ser. No. 36,430, filed on May 11, 1970, now US. Pat. No. 3,697,683

This invention relates to phosphate derivatives of barbiturates. In one aspect, this invention relates to 3- N-alkyl phosphate derivatives of barbituric acids. In another aspect this invention relates to the use of these compounds as pesticides and more particularly as insecticides and miticides.

The compounds of the subject invention are characterized by the following structural formula:

wherein R and R are each selected from the group consisting C,C alkoxy, C C thioalkyl, C -C alkyl, C C alkoxyalkyl, phenyl, phenoxy, thiophenyl, wherein said groups can be optionally substituted with chlorine, bromine, nitrile or nitro; R and R may or may not be the same; R is one selected from the group consisting of hydrogen, C -C alkyl, optionally substituted with chlorine or bromine; R is one selected from the group consisting of hydrogen, C -C alkyl, optionally substituted 'with chlorine or bromine, phenyl, bromo or chlorosubstituted phenyl, C C alkylamino, C C dialkylamino, C C acyl, C -C thioalkyl, C -C alkylsulfoxide, C C, alkylsulfone, C -C alkoxyalkyl, C C alkenyl, C -C alkynyl; R and R are each selected from the group consisting of C,C alkyl, phenyl, C C chloro or bromo-substituted alkyl, C -C alkylthio, thiophenyl optionally substituted by chlorine, bromine, C,-C alkyl or nitro, C C alkylsulfoxide, C C alkylsulfonyl, C -C alkoxy, C C alkoxyalkyl, C -C monoalkylamino and C C dialkylamino, cyano, thiocyano, C -C alkenyl, C C alkynyl, nitro, C -C cycloalkyl and C C cycloalkenyl wherein R and R may. or may not be the same; X and Y can be O or S; and n is an integer ranging from 1 to 3. Such compounds have been found to possess highly active contact and systemic insecticidal and miticidal activity.

Exemplary of those compounds coming within the scope of this invention are the following: l. S-[ l,S-diethyl-5-methylmercaptobarbituryl-3-( 1- ethyl -O-ethyl-S-methylphosphorodithioate 2. S-[ l-methyl-5,5-diethylbarbituryl-3-methyl]-0,0- dimethylphosphorothioate 3. S-[ 1,5 ,5-trimethylbarbituryl-S-methyl]-ethyl-O- ethyl-phosphonodithioate 4. S-[ 1,5-dimethyl-5-( l-cyclohexenyl)barbituryl-3- methyl1-O-ethyl-S-propylphosphorodithioate 5. S-[ 1 -ethyl-5-methyl-5-ethylbarbituryl-3-(2- chloroethyl ]-0,0-dimethylphosphorothioate 6. S-[ l-allyl-5-methyl-5-prop.ylbarbituryl-3-( l-ethyl)]- O-ethyl-S-cycloexylphosphorodithioate 7. S-[ l-methyl-5,5-dimethylmercaptobarbituryl-3-(2 bromoethyl)]-phenyl-O-ethylphosphonothioate 8. S-] l-propargyl-5-propyl-5-cyanobarbituryl-3- benzyll-O-methyl-S-phenylphosphorodithioate 9. S-[l-ethoxy-5-ethyl-5rthiocyanobarbituryl-3-(4 bromobenzyl) ]-O-phenyl-S-propylphosphorodithioate 2 10. S-[ l,5-dimethyl-5-dimethylaminobarbituryl-3- methyl]-O-ethyl-O-4-chlorophenylphosphorothioate l l. S-[ l-(2-methoxyethyl)-5-(2-chloroethyl)-5- methylsulfonyl-barbituryl-3-(2-ethyl)]-0,0- dimethylphosphorothioate 12. S-[ l-( 2-methylmercaptoethyl )'-5 -methyl-5- cyclopentylbarbituryl-3-methyll-O-cyclohexyl-S- propylphosphorodithioate 13. S-[ 1-phenyl-5-ethoxy-5-methylsulfinylbarbituryl-3- (3-propyl) -cyclopentyl-O-propylphosphonodithioate 14. S-[ l,S-dimethyl-5-propylbarbituryl-3-methylJ- 0,0-dimethylphosphorothioate 15. S-[ 1-methylsulfonyl-S-methyl-5-phenylbarbituryl- 3-methyl]-0,0-diethylphosphorothioate 16. S-[ l-dimethylamino-5-propargyl-5-( 4- chlorophenyl )barbituryl-3-methyl ]-O-ethyl-S- propylphosphorodithioate 1 17. S-[ l-acetyl-5-ethyl-5-(2-methoxyethyl )barbituryl- 3-( 2-ethyl -0,0-dimethylphosphorothioate 18. S-[ 1-( 2-chloroethyl )-5-methyl-5-nitrobarbituryl-3- methyl ]-S,S-dipropylphosphorotrithioate f 19. S-[ 1,5 ,5-trimethylbarbituryl-3-methyl]-0,0- is hylp q ahq q 1 20. S-[ l ,5,S-trimethylbarbituryl-3-methyl ]-0,0-

diethylphosphorodithioate I 21. s-' 1 5,5-trimethylbarbituryl-3-methyl]-0,0- dimethylphosphorodithioate E22. 5 i S -fl ,5,5-trinithylbarbiiuryl-3methyl]-0,0- isiimetbylplzqsp sirothw ts. 23. S-[ l,5,S-trimethylbarbituryl-3-methyll-O-ethyl-S- p py p p o thbg q., 24. S -T l ,5 -dimethyl-5-( l-cyclohexenyl)barbituryl-3- methyl]-O,O-dimethylphosphorothioate 25. S-[ l,5-dimethyl-5-( l-cyclohexenyl )barbituryl-3- EE QQJIQ1QZl FlIYLB L EPLQEEDLQE .26.

S.-[ 1,5-dimethyl-5-( l-cyclohexenyl )barbituryl-3- I methyl]-0,0-dimethylphosphorodithioate WM mm 1 27. S-[1,5-dimethyl-5-( l-cyclohexenyl)barbituryl-3- methyl]-O,O-diethydphosphorodithioate V S-[ l ,5-dimethyl-5-( l-cyclohexenyl )bar biu ry l-3 methyl ]-ethyl-O-ethylphosphonodithioate i lylarrzmp sgb qd tyoate 30. S-[ l-methyl-5,5-diethylbarbituryl-3-methyll-ethyl- Qfll YIEWSBl QPPFl LhP??? 31. S-ll-methyl-5-ethyl-5-pheiiylbarbituryl lfmethyl1 Q,Q-dimethylphosphorothioate V g w 32. S.-[ 1-methyl-5,S-diethylbarbituryl-3-methyl ]-0,0- diethylphosphorothioate 33. s-'[ I -rne thyI S JS-diethylbarbituryl 3-methyl]-O,O

, diethylpliosphorodithioate 34, sl-methyl-5,S diethylbarbituryI-3-methyl1 6,6

dimethyl phosphorodithioate The foregoing compounds can bereadily prep ai'edby ;the following method which is represented schematically:

" nn on.

I H NCH 0H CH3 CH3" 2 CH3 CH3 A B o y -s-niihyilof f I' earth, or flours such as walnut shell, wheat, redwood, N N 0 soya bean, and cottonseed flours. Other inert solid conso C12 ditioning agents or carriers of the kind conventionally CH3 NCHQOH CH3 NCHzCl 5 employed in preparing pest control compositions in OH I OH powdered from can be used.

3 0 Granulars can be compounded by adsorbing the C D E compound in liquid form onto a preformed granular diluent. Such diluents as natural clays, pyrophyllite, di-

CH: CH: atomaceous earth, flours such as walnut shell, as well l l as granular sand can be employed. 0 0 Y B1 In addition, granulars can also be compounded by ad- NCH C1 PXM [1 mixing the active ingredient with one of the powdered CH: CH5 NCHX diluents described hereinabove, followed by the step of (Misamonovalent either pelleting or extruding the mixture.

a 0 i Liquid compositions of the invention are prepared in E F G a the usual way be admixing one or more of the active in Reactunts Mole Ratios Temp. (C) Pressure (Atm) Solvent A B l:l-l 1s 80-[20 1-10 ,0. Dimethylsulfoxides, ethanol Preferred l :3 I00 1 H1O C D l:l-l:5 -100 l-lO Benzene. toluene.

chloroform. methylene chloride Preferred 1:2 60-80 1 chloroform E F l:l-l.5 -l00 l-lO chloroform. benzene, nethylene chloride, acetonitrile, toluene, xylene, tetrahydrot'uran Preferred 1:l.l 80 l acetonitrile Preparation of 1,5,5-trisubstituted barbituric acids (Reagent A) are well documented in the chemical literature, and form no part of the present invention.

Compounds characterized by the structural formula:

wherein R R and R are as defined hereinbefore, and X is either 0 or S, novel and find utility as intermediates in the preparation of the compounds of the subject i rsmiontthey 259129 59 3. 9i fussisi e astiyitt The compounds of the invention have general insecticidal properties.

Insecticidal compositions of the invention are prepared by admixing one or more of the active ingredients defined heretofore, in insecticidally effective amounts with a conditioning agent of the kind used and referred to in the art as a pest control adjuvant or modifier to provide formulations adapted for ready and efficient application using conventional applicator equipment.

Thus, the insecticidal compositions or formulations are prepared in the form of solids or liquids. Solid com-.

positions are preferably in the form of granulars dusts.

The compositions can be compounded to give homogeneous free-flowing dusts by admixing the active comgredients with a suitable liquid diluent mediumfln the ,cases where the compounds are liquids, they may be sprayed in ultra low volume as such. With certain solvents, such as alkylated naphthalene or other aromatic petroleum solvents, dimethyl formamide, cycloketone, relatively high up to about 50 percent by weight or more concentration of the active ingredient can be ob- 40 tained in solution.

The insecticidal compositions of the invention,

whether in the form of dusts or liquids, preferably also include a surface-active agent sometimes referred to in the art as a wetting, dispersing, or emulsifying agent.

; These agents, Which will be referred to hereinafter Tmore simply as 'surfaceactive dispersing agents, cause the compositions to be easily dispersed in water to give aaqueous sprays which, for the most part, constitute a desirable composition for application.

The surface-active dispersing agents employed can be of the anionic, cationic, or nonionic type and in clude, for example, sodium and potassium oleate, the amine salts of oleic acid, such as morpholine and dimethylamine oleates, the sulfonated animal and vegeta- 1ble oils, 'such as sulfonated fish and castor oils, sulfohyde, sodium lauryl sulfate, disodium monolauryl phosphate, sorbitol laurate, pentaerthritol monostearate, glycerol monostearate, diglycol oleate, polyethylene oxides, ethylene oxide condensation products with stearyl alcohol and alkylphenol, polyvinyl alcohols, salts, such as the acetate of polyamines from reductive amination of ethylene/carbon monoxide polymers, laurylamine hydrochloride, laurylpyridinium bromide,

stear l. t ims't y m o m bwm de cewldimethyl;

the compositions as actually applied for destroying in-- sects will vary with the manner of application, the particular insects for which control is sought, the purpose for which the application is being made, and like variables. In general, the insecticidal compositions as applied in the form of a spray, dust or granular, will contain from about 0.1 percent to 100 percent by weight of the active compound.

Fertilizer materials, other insecticidal agents, andother pest control agents such as herbicides and fungicides can be included in the insecticidal compositions of the invention if desired.

The term carrier" or diluent as used herein means a material, which can be inorganic or organic and synthetic or of natural origin, with which the active ingredient is mixed or formulated to facilitate its storage, transport, and handling and application to the plants to be treated. The carrier is preferably biologically and chemically inert and, as used, can be a solid or fluid. When solid carriers are used, they are preferably particulate, granular, or pelleted; however, other shapes and sizes of solid carrier can be employed as well. SUch preferable solid carriers can be natural occurring minerals although subsequently subjected to grinding, sieving, purification, and/or other treatments including, for example, gypsum; tripolite; diatomaceous earth; mineral silicates such as mica, vermiculite, talc, and pyrophyllite; clays of the montomorillonite, kaolinite, or attapulgite groups; calcium or magnesium limes, or calcite and dolomite; etc. Carriers produced synthetically, as for example, synthetic hydrated silica oxides and synthetic calcium silicates can also be used, and many proprietary products of this type are available commercially. The carrier can also be an elemental substance such as sulfur or carbompreferably 5123c;

tivated carbon. l f t he carrier possesses intrinsic catalytic activity such that it would decompose the active ingredient, it a advantageous to incorporate a stabilizing agent, as for example, polyglycols such as diethylene glycol, to neutralize this activity and thereby prevent possible decomposition of the derivatives of the present nitrated aryl compounds. 7

For some purposes, a resinous or waxy carrier can be used, preferably one which is solvent soluble or thermoplastic, including fusible. Examples of such carriers are natural or synthetic resins such as a coumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride, styrene polymers and copolymers, a solid grade of polychlorophenol such as is available under the registered trademark Aroclor, a bitumen, an asphaltite, a wax for example, beeswax or a mineral wax such as paraffin wax or montan wax, or a chlorinated mineral wax, or a microcrystalline wax such as those available under the registered trademark MikrovanWax. Compositions comprising such resinous or waxy carriers are preferably in granular or pelleted form.

Fluid carriers can be liquids. as for example, water, or an organic fluid. including a liquefied normally vaporous or gaseous material, or a vaporous or gifi material, and can be solvents or nonsolvents for the active material. For example, the horticultural petroleum spray oils boiling in the range of from about 275 to about 575F., or boiling in the range of about 575 to about 1,000F. and having an unsulfonatable residue of at least about percent and preferably of at least 1 about 90 percent, or mixtures of these two types of oil,

fare particularly suitable liquid carriers.

The carrier can be mixed or formulated with the active material during its manufacture or at any stage subsequently. The carrier can be mixed or formulated with the active material in any proportion depending on the nature of the carrier. One or more carriers, moreover, can be used in combination.

The compositions of this invention can be concentrates, suitable for storage or transport and containing, for example, from about 5 to about 90 percent by weight of the active ingredient, preferably from about v 20 to about wt. percent. These concentrates can be diluted with the same or different carrier to a concentration suitable for application. The ccompositions of this invention may also be dilute compositions suitable for application. In general, concentrations of about 0.l to about 10 percent by weight, of active material based on the total weight of the composition are satisfactory, although lower and higher concentrations can be applied if necessary.

The compositions of this invention can also be formulated as dusts. These comprise an intimate admixture of the active ingredient and a finely-powdered solid carrier such as aforedescribed. The powdered carriers can be oil-treated to improve adhesion to the surface to which they are applied. These dusts can be concentrates, in which case a highly-sorptive carrier is preferably used. These require dilution with the same or a different finely-powdered carrier, which can be of lower sorptive capacity, to a concentration suitable for application.

The compositions of the invention can be formulated as wettable powders comprising a major proportion of the active ingredient mixed with a dispersing, i.e., deflocculating or suspending agent, and if desired, a finely-divided solid carrier and/or a wetting agent. The ac; tive ingredient can be in particulate form or adsorbed on the carrier and preferably constitutes at least about 10 percent, more preferably at least about 25 percent, by weight of the composition. The concentration of the dispersing agent should in general be between about 0.5 and about 5 percent by weight of the total composition, although larger or smaller amounts can be used if desired.

The dispersing agent used in the composition of this invention can be any substance having definite dispersing, i.e., deflocculating or suspending, propertiesas distinct from wetting properties, although these substances can also possess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids such as gelatin, glue, casein, gums, or a synthetic polymeric material such as polyvinyl alcohol and methyl cellulose. Preferably, however, the dispersants or dispersing agents used are sodium or calcium salts of high molecular weight sulfonic acids, as for example, the sodium or calcium salts of lignin sulfonic acids derived from sulfite cellulose waste liquors.

The calcium or sodium salts of condensed aryl sulfonic acid. for example. the products known as Tamol 731, are also suitable.

The setting agents used can be nonionic type surfacpolymers, commercially known as Pluronics can be used. Partial esters of the above acids with polyhydric alcohols such as glycerol, polyglycerol, sorbitol, or mannitol can also be used.

Suitable anionic wetting agents include the alkaliv metal salts, preferably sodium salts, of sulfuric acid esters or sulfonic acids containing at least carbon atoms in a molecule, for example, the sodium secondary alkyl sulfates, dialkyl sodium sulfosuccinate available under the registered trademark Teepol, sodium salts of sulfonated castor oil, sodium dodecyl benzene sulfonate.

Granulated or pelleted compositions comprising a suitable carrier having the active ingredient incorporated therein are also included in this invention. These can be prepared by impregnating a granular carrier with a solution of the inert ingredient or by granulating a mixture of a finely-divided solid carrier and the active ingredient. The carrier used can consist of or contain a fertilizer or fertilizer mixture, as for example, a superphosphate.

i The compositions of this invention can also be formulated as solutions of the active ingredient in an organic solvent or mixture of solvents, such as for example, alcohols; ketones, especially acetone; ethers; hydrocarbons, etc.

Where the toxicant itself is a liquid these materials can be sprayed on crops or ins ects without further dilution.

Petroleum hydrocarbon fractions used as solvents should preferably have a flash point above 73F., an example of this being a refined aromaticextractpf kero; Esene. Auxiliary solvents such as alcohols, ketones, and polyalkylene glycol ethers and esters can be used in conjunction with these petroleum solvents.

Compositions of the present invention can also be formulated as emulsifiable concentrates which are concentrated solutions or dispersion of the active ingredient in an organic liquid, preferably a water-insoluble organic liquid, containing an added emulsifying agent. These concentrates can also contain a proportion of water, for example, up to about 50 percent by volume, based on the total composition, to facilitate subsequent dilution with water. Suitable organic liquids include, e.g., the above petroleum hydrocarbon fractions previously described. g WW The emulsifying agent can be of the type producing water-in-oil type emulsions which are suitable for application by low volume spraying, or an emulsifier of the type producing oil-in-water emulsions can be used, producing concentrates which can be diluted with relatively large volumes of water for application by high volume spraying or relatively small volumes of water for low volume spraying. In such emulsions, the active ingredient is preferably in a nonaqueous phase.

The present invention is further illustrated in greater" detail by the following examples, but it is to be understood that the present invention in its broadest aspects, is not necessarily limited in terms of the reactants, or specific temperatures, residence times, separation techniques and other process conditions, etc.; or dosage level, exposure times, test plants used, etc. by which the compounds and/or compositions described and claimed are prepared and/or used.

EXAMPLE 1 Preparation of l ,5,5-Trimethyl-3 -Chloromethylbarbituric Acid A mixture of 32.0 g. (0.15 mole) of 1,5,5-trimethyl- "barbituric acid and 50 g. (0.56 mole) of 37 percent aqueous formaldehyde in 300 ml. of water was heated to reflux for 16 hours. The water was removed in vacuo, the residue taken up in 250 ml. of chloroform,. dried (MgSO and the solvent removed in vacuo to give 40.7 g. of crude hydroxymethylated product. This wastaken up in 100 ml. of chloroform, 30 ml. (0.45

mole) of thionyl chloride was added and the mixture heated to reflux for 3 hours. The solvent was removed in vacuo, the residue taken up in toluene, washed 4 times with 50 ml. of water and dried (MgSO The solvent was removed in vacuo to afford 28.1 g. of yellow oil, whose infrared and nmr spectra confirmed the structure.

EXAMPLE 2 Preparation of 1,5 dimethyl-3-chloromethyl-5-( lcyclohexenyl) barbituric Acid A mixture of 246 g. (1.05 mole) of l,5-dimethyl-5- (l-cyclohexenyl barbituric acid, 230 ml (3.0 mole) of 37 percent aqueous formaldehyde, 300 ml of water and 500 ml of ethanol was heated to reflux for 18 hours.

The lower phase was separated, dissolved in 500 ml of chloroform, dried (MgSO and the solvent removed to afford 254 g. of crude hydroxymethylated material. To 100 g. (0.38 mole) of the latter dissolved in 600 ml of chloroform was added ml (0.75 mole) of thionyl chloride, the mixture heated to reflux for 3 hours, the solvent stripped, the residue triturated with toluene and filtered. The filtrate was stripped in vacuo to afford 60.4 g. of a viscous oil, whose nmr and infrared spectra confirmed the structure.

Anal: Calcd, for C,,H,,N,0,Cl; C,54.98; H,5.98;

N,9.85 Found: C,56,09; H,6.06; N,l0.97

EXAMPLE 3 was added 3.02 g. (0.019 mole) of ammonium O -dimethylphosphorothioate. The mixture was S-l 1,5,5-Trimethylbarbituryl-3- EXAMPLE Preparation of S-[ l ,5 ,5-Trimethylbarbitury1-3- Methyl1-O-Ethyl-S-Propylphosphorodithioate (Cpd.23)

This compound was prepared according to procedures set forth in Example 4. The product was an oil, whose nmr and infrared spectra confirmed the structure.

Anal. Ca1cd.: C, 40.95; H, 6.05; N, 7.32

Found: C, 42.28; H, 6.37; N, 8.02

EXAMPLE 6 Preparation of S-[ 1,5 ,5-Trimethylbarbituryl-3- Methyl]-0,0-Diethylphosphorothioate (cpd. 19)

This compound was prepared according to proce dures set forth in Example 4. The product was an oil, whose nmr and infrared spectra confirmed the structure.

Anal. Calcd.: C,40.8;H,5.95;N,7.95 Found: C,39.27;H,5.99;N,6.73

EXAMPLE 7 Preparation of S-[ 1,5,5-Trimethylbarbituryl-3- Methyl]-0,0-Diethylphosphorodithioate (cpd. 20)

This compound was prepared according to procedures set forth in Example 4. The product was an oil, whose nmr and infrared spectra confirmed the structure.

EXAMPLE 8 Preparation of S-[ 1,5 ,5-Trimethylbarbituryl-3- Methyl]-0,0-Dimethylphosphorodithioate (cpd. 21)

This compound was prepared according to procedures set forth in Example 4. The product was an oil, whose nmr and infrared spectra confirmed the structure.

EXAMPLE 9 Preparation of S-[ 1,5-Dimethyl-5-( 1-Cyclohexenyl)- Barbitury1-3-Methyl]-0,0-Dimethylphosphorodithioate (cpd. 26)

This compound was prepared according to procedures set forth in Example 4. The product was an oil,

whose nmr and infrared spectra confirmed the structure.

Anal. Calcd: C,44.31;H,5.66;N,6.91;P,7.65 Found: C,44.18;H,5.91;N,6.81;P,7.02

EXAMPLE 10 Preparation of S-[ 1,5-Dimethy|-5-( l-Cyclohexenyl)- Barbituryl-3-Methyl]-O-Ethyl-S-Propy1phosphorodiothioate (cpd. 4)

This compound was prepared according to procedures set forth in Example 4. The product was an oil,

whose nmr and infrared spectra confirmed the structure.

Anal. Calcd.: C,45.58; H,6.51; N,6.25

Found: C,46.67; H,6.l6; N,6.20

EXAMPLE 10a Preparation of S-[1-Methy1-5,5-Diethyl-Barbituryl-3- Methyl]-0,0-Dimethylphosphorothioate (Cpd. 2)

The compound was prepared according to the procedures set forth in Example 4. The product was an oil, whose nmr and infrared spectra confirmed the structure.

EXAMPLE 10b Preparation of S-l1-Methyl-5,5-Diethyl-Barbituryl-3- Methyl]-O-Ethyl-S-propylphosphorodiothioate (Cpd. 29)

The compound was prepared according to procedures set forth in Example 4. The product was a viscous oil, whose nmr and infrared spectra confirmed the structure.

Anal. Calcd. for C H N O PS C. 43.81; H, 6.58;

N, 6.83 Found: C, 44.20; H, 6.50; N, 7.80

EXAMPLE 1 1 Preparation of S-[ 1,5-Dimethy1-5-( l-Cyc1ohexenyl)- Barbituryl- 3-Methyl]-0,0-Diethy1phosphorothioate (cpd. 25)

The compound was prepared according to procedures set forth in Example 4. The product was an oil, whose nmr and infrared spectra confirmed the structure.

Anal. Calcd: C,48.80; H,6.45; N,6.7l

Found: C,46.13; H,6.l6; N,6.61

EXAMPLE 12 Preparation of S-l1,5-Dimethy1-5-(l-Cyclohexenyl)- Barbituryl-3-Methyl]-0,0-Diethylphosphorodithioate (cpd. 27)

The compound was prepared according to procedures set forth in Example 4. The product was a viscous oil, whose nmr and infrared spectra confirmed the structure.

EXAMPLE 13 Preparation of S-[ 1,5-Dimethyl-5-( lCyclohexenyl)- Barbituryl-3-Methyl]-0,0-Dimethylphosphorothioate (cpd. 24)

The product was prepared according to the procedures set forth in Example 4. The product was a viscous oil, whose nmr and infrared spectra confirmed the structure.

EXAMPLE 14 Preparation of S-[ 1,5,5-Trimethy1barbituryl-3- Methyl]-Ethy1-O-Ethylphosphonodithioate (Cpd. 3)

To a solution of 4.0 g. (0.0183 mole) of 1,5,5- trimethyl-3-chl0romethylbarbituric acid and 3.12 g. (0.0183 mole) of ethyl O-ethyldithiophosphonic acid 'in ml of acetonitrile was added dropwise, with stirring, a solution of 1.85 g. (0.0183 mole) of triethylamine in 10 ml. of acetonitrile. The solution was stirred at room temperature for 1 hour, then heated to reflux for 2 hours. The solvent was removed in vacuo, the residue taken up on 300 ml. of benzene and filtered. The filtrate was washed successively with 50 ml. of water, 50 ml. of a saturated sodium bicarbonate solution, and twice with 50 ml. of water. After drying (MgSO the solvent was removed in vacuo and placed under high vacuum (0.1 mm) for 1 hour to afford 4.1 g. of a light yellow oil whose infrared and nmr spectra confirm the structure.

Anal. Calcd. for C H N O PS C, 40.9l; H, 5.96;

MITES, CONTACT Potted bean plants infested with the two-spotted spider mites were placed on a turntable and sprayed with a mu a on. qflh 19s! s s isa t he pla t r methyll-ethylTO-ethyl-phosphonodithioate held for seven days and thedegree of mite control was N,7.9l,P, 8.80 d f d Found: C, 41.57; H, 6.57; N, 5.87; P, 9.03 rate a PerJ EXAMPLE MITEs; SYSTEMIC Preparation of S-[1-Methyl-5,5-Diethylbarbituryl-3- Bean 1 d b 1 20 1 f h 15 p ants were treate y app ying m o t e Methyl]-Ethyl-O-Ethylphosphonodithioate (C formulated test chemical to the soil. The mites were The above m n was prepared accordmg to the transferred to the plant after 24 hours. The plants were procedure Outlmed m Example The product was I held for seven more days and the degree of mite control a yellow Oll, whose infrared and nmr spectra confirm rated the structure. y

EXAMPLE 16 APHID, CONTACT Potted nasturtium plants infested with the bean Preparanon of h i l'l l a aphids were placedon a turntable and sprayed with a Cyclohexenyl)Bafblluryls'Met y t y formulation of the test chemical. The plants were held Ethylphosphonodlthloate (Cpd- 28) I for two days and the degree of aphid control was rated.

The above compound was prepared accordmg to the procedures outlined in Example 14. The Product was a yellow oil whose infrared and nmr spectra confirm APHID, SYSTEMIC the Structure- Nasturtium plants were treated by applying 20 ml. of GENERAL EXPERIMENTAL PROCEDURES FOR 30 the formulated test chemical to the SOll. The aphids BIOLOGICAL TESTING were transferred to the plants after 24 hours. The h f n h b h plants were held for 48 addltional hours and the degree In the examples whIc o ow, t e ar Iturate p osof the Aphid control rated phates were treaterd In the greenhouse and In the laboratory to determine their biological activity.

The experimental compounds were tested as aqueous HOUSEFLY emulsions. These emulsions were prepared by dis- Caged houseflles were sprayed with the formulated solving the compound in acetone and dispersing it in test chemical. After 2 days the degree of housefly condistilled water with Triton X-lOO, an alkylaryl polytrol was rated. ether alcohol derived by the reaction of i-cetyl phenol with ethylene oxide, to give spray emulsions containing 40 BOLL WEEVIL the desired concentration of the compound. These Five mixed sex adult Boll weevils placed in a wire emulsions were then used in standard laboratory tests screen cage were sprayed with the proper concentradescribed below. tion of formulated test chemical. The boll weevils were provided with sucrose solution on a filter paper. The MEXlCAN BEAN BEETLE cages were held at about 70F. for 24 hours and the Bean leaves were dipped in the emulsion of the test percent mortality read after 24 hours.

if A A 7 TAFIEI BIOLOGICAL ACTIVITY OF BARBITURATE PHOSlATE? I I Com- Mex. Southern Mite Ii/in Aphid Boll pound Bean Army Contact Systemic Con- Syswee- No. Compound Beetle Worm Adult Nymph Adult Nymph tact vil emu:

22 S4 l.5.5-trimethylbarbituryl-3- I00 0 100 I00 I00 I00 I00 90 so 100 methyl]-0.()-dimethylphosphoroll 1 23 :5 .5-trimethylbarbitury|-3- I00 I00 I00 100' I00 90 50 I00 methyl]-Oethyl-S-propylphos phorodithioate 21 s-[ l.5.5-trimethylbarbituryI-3- I00 o 100 I00 I00 I00 20 methyl]-O O-dimethylphosphorodithioatc 20 S-ll.5.5-trimethylbarbituryl-3- I00 0 I00 I00 I00 I00 30 0 methyl]-0,0-dicthylphosphorodithioate l9 s-[ l.5.5-trimethylbarbituryl-3- 100 0 I00 I00 I00 I00 70 methyl]-0.0-diethylphosphor0 thioate I 3 s-[ l.5.5-trimethylbarbituryl-3- I00 I00 I00 I00 90 90 I00 60 3,839,335 13 14 ""TABLE I-Continued BIOLOGICAL ACTIVITY OF BARBITURATE PHOSPHATES- 7zControl Com- Mex. Southern Mite Mite Aghid Boll pound Bean Army Contact Systemic Con- Sysweeouse No. Compound Beetle Worm Adult Nymph Adult Nymph tact -Fly vil emic 4 S-llj-dimethyl-S-ELcylohek- 100 100 90 30 '0 0 enyl)barbituryLS-methyl]-O- ethyl-S-propylphosphorodithioate I S-[ I ,5-dimethyl-5-( l-cyclohex- 60 0 20 l0 l0 0 20 10 enyl)barbituryl-3 methyl]-0.0- diethylphosphorothioate 27 S-ll,5-dimethyl-5-(l-cyclohexenyl) 100 0 30 I0 0 0 O 0 barbituryl-3-methyl]0.0-diethylphosphorodithioute 26 S-[ l.5-dimethyl-5-( l-cyclohexenyl) I00 0 l0 0 0 0 20 0 barbituryI-S-methyl] 0.0-dimethylphosphorodithioate 24 S-[ l.5-dimethyl-5-( l-cyclohexenyl) 100 0 l0 0 100 100 0 20 barbituryl-3-methyl]O O-dimethylphosphorothioate 28 S-[ l.5-dimethyl-5-( l-cyclohexenyl) I00 0 40 20 0 0 10 50 barbituryl-3-methyl]-ethyl-O-ethylphosphonodithioate 2 S-ll-methyl-5,5-diethylbarbituryltoo 20 100 100 100 100 50 20 3-methyl]-0.0-dimethylphosphorothioute 29 S-[ lmethyl-5.5-diethylburbituryl- 60 100 0 0 O 0 90 40 3-methyl] O-ethyl-S-propylphosphorodithioate 3O Sll-methyl-55-diethylbarbituryl- 100 0 100 I00 10 0 I00 40 3-methyl]-ethylo-ethylphosphonodithioate All tests except Southern Army Worm were run at 250 ppm concentration Southern Army Worm was run at 500 ppm concentration What is claimed is: 3. l-miHyl--c hTorbtnethyl-5,S-dithylbarbituric l. l,5,5-tr1methyl-3-chloro-methylbarbituric acid. acid. 2. l,5-dimethyl-3-chlor0methy]-5-( 1-cycl0hexenyl)- barbituric acid. 1k J ,3 35 

1. 1,5,5-TRIMETHYL-3-CHLORO-METHYLBARBITURIC ACID.
 2. 1,5-dimethyl-3-chloromethyl-5-(1-cyclohexenyl)barbituric acid.
 3. 1-methyl-3-chloromethyl-5,5-diethylbarbituric acid. 